Preparation of substituted tetrazolinones

ABSTRACT

Substituted tetrazolinones exhibit usefulness as pre-emergent herbicides, post-emergent herbicides and plant growth regulators.

This is a division application of U.S. patent application Ser. No.737,371 filed May 23, 1985, U.S. Pat. No. 4,826,529 which is acontinuation of copending U.S. patent application Ser. No. 560,031 filedDec. 9, 1983, now U.S. Pat. No. 4,618,365.

BACKGROUND OF THE DISCLOSURE

1. Field of the Invention

The instant invention is directed to a new class of substitutedtetrazolinone compounds. More specifically, the instant inventionrelates to a new class of substituted tetrazolinone compounds which areuseful as preemergence herbicides, post-emergence herbicides, and/or asplant growth regulators.

2. Background of the Prior Art

The synthesis of certain substituted tetrazolinones is known in the art.Thus, Horwitz, et al, JACS, 81 3076 (1959) and Tsuge et al, J. Org.Chem., 45 5130 (1980) provide methods for synthesizing tetrazolinones.These disclosures provide no utility for the classes of substitutedtetrazolinones synthesized.

The need for effective herbicides, both preemergence and post-emergenceneeds no special emphasis. The control of weeds and undesirablevegetation is of great economic importance since weed competitioninhibits the production of foliage, fruit or seed of agricultural crops.The presence of weeds can reduce harvesting efficiency and the qualityof the harvested crop. Weed control is essential for maximum productionof many agronomic and horticultural crops including corn, (Zea mays L.), cotton (Gossypium SP), sunflower (Helianthus annus L.) and soybeans(Glycine max (L.) Merr.). Weeds on noncropped areas may cause a firehazard, undesirable drifting of sand or snow, and/or irritation topersons with allergies. Thus, suppression of undesirable weed growth isvery advantageous.

Moreover, the need for agricultural chemicals having significant effectson the growth and development of crop plant species is similarly wellknown. Thus, for many crops, it is highly desirable that certain plantgrowth regulatory effects by accomplished. In general, these growthregulatory effects include one or more of the following: dwarfing,cessation of terminal growth, inhibition or stimulation of axillary andintercalary growth, retardation or stimulation of internode elongation,inhibition or stimulation of flowering or reproductive development, andthe like.

SUMMARY OF THE INVENTION

It has now been found that a new class of substituted tetrazolinonesunexpectedly provides excellent pre-emergence and post-emergenceherbicidal properties and/or plant growth regulatory effects.

In accordance with the instant invention, a compound having the formula:##STR1## wherein R is:

C₁ -C₁₂ alkyl,

C₂ -C₁₃ alkoxyalkyl,

C₇ -C₉ aralkyl,

C₅ -C₆ cycloalkyl,

C₃ -C₁₂ alkenyl,

naphthyl,

phenyl,

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

NR³ R⁴ wherein R³ and R⁴ are the same or different and are hydrogen orC₁ -C₆ alkyl,

C₂ -C₅ alkoxycarbonyl,

carboxy,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio; or

benzyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

C₂ -C₅ alkoxycarbonyl,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio;

R¹ and R₂ are the same or different and are:

C₁ -C₆ alkyl,

C₃ -C₆ alkenyl,

C₅ -C₆ cycloalkyl,

C₇ -C₉ aralkyl,

C₇ -C₉ aralkyl substituted with at least one member selected from thegroup consisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine,

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

methylenedioxy,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene; or

naphthyl,

phenyl, or

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine;

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenyl,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

nitro,

C₁ -C₂ alkylenedioxy, optionally substituted with 1-2 methyl groups,

C₁ -C₂ alkyleneoxy, optionally substituted with 1-2 methyl groups,cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene; or

R¹ and R² together are C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene,

is disclosed.

In further accordance with the instant invention a composition isprovided comprising the compound of this invention with a carrier.

In still further accordance with the present invention a method forcontrolling weeds and undesirable vegetation employing the compositionof this invention is taught.

In yet further accordance with the present invention, a method forregulating the growth of plants employing the composition of thisinvention is taught.

DETAILED DESCRIPTION

The present invention is directed to a compound having the structuralformula: ##STR2## wherein R is:

C₁ -C₁₂ alkyl,

C₂ -C₁₃ alkoxyalkyl,

C₇ -C₉ aralkyl,

C₅ -C₆ cycloalkyl,

C₃ -C₁₂ alkenyl,

naphthyl,

phenyl,

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

NR³ R⁴ wherein R³ and R⁴ are the same or different and are hydrogen orC₁ -C₆ alkyl,

C₂ -C₅ alkoxycarbonyl,

carboxy,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio; or

benzyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₄ alkyl,

C₁ -C₄ alkoxy,

methylenedioxy,

C₂ -C₅ alkoxycarbonyl,

phenoxy,

nitro,

cyano,

trihalomethyl wherein halo is fluorine, chlorine or bromine,

trihalomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkylthio, and

C₁ -C₆ fluoroalkylthio;

R¹ and R₂ are the same or different and are:

C₁ -C₆ alkyl,

C₃ -C₆ alkenyl,

C₅ -C₆ cycloalkyl,

C₇ -C₉ aralkyl,

C₇ -C₉ aralkyl substituted with at least one member selected from thegroup consisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine;

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

methylenedioxy,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene: or

naphthyl,

phenyl,

phenyl substituted with at least one member selected from the groupconsisting of:

fluorine,

chlorine,

bromine,

iodine,

C₁ -C₆ alkyl,

C₁ -C₂ haloalkyl wherein halo is fluorine, chlorine or bromine:

halomethoxy wherein halo is fluorine, chlorine or bromine,

C₁ -C₆ alkoxy,

C₁ -C₆ alkylthio,

C₁ -C₆ fluoroalkylthio,

phenoxy,

phenyl,

phenylthio,

carboxy,

C₂ -C₅ alkoxycarbonyl,

C₁ -C₂ alkylenedioxy, optionally substituted with 1-2 methyl groups,

C₁ -C₂ alkyleneoxy, optionally substituted with 1-2 methyl groups,

nitro,

cyano, and

NR⁷ R⁸ wherein R⁷ and R⁸ are the same or different and are hydrogen, C₁-C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene; or

R¹ and R₂ together are C₄ -C₈ alkylene or C₄ -C₈ oxydialkylene.

Among the more preferred compounds of this invention are those wherein:

R is

C₁ -C₄ alkyl,

phenyl, or

phenyl substituted with at least one member of the group consisting of:

C₁ -C₃ alkyl and

C₁ -C₃ alkoxy;

R₁ is C₁ -C₄ alkyl; and

R₂ is

phenyl or

phenyl substituted with at least one member of the group consisting of:

C₁ -C₃ alkyl,

C₁ -C₃ alkoxy,

chlorine, and

trihalomethyl.

Particularly preferred compounds include:

1-methyl-4-[(N-isopropyl, N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-ethyl-4-[(N-isopropyl, N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-n-propyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-n-butyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-[2-methyl]phenyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-[4-chloro]phenyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-methyl)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-methoxy)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,and

1-(2,6-dimethyl)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone.

More preferably, when the compound of this invention is to be employedas a plant growth regulator, the invention is directed to a compoundhaving the structural formula given above wherein

R is:

C₁ -C₄ alkyl,

C₇ -C₉ aralkyl,

naphthyl,

phenyl, or

phenyl substituted with one or more members of the group consisting of:

fluorine,

chlorine,

bromine,

C₁ -C₃ alkyl,

C₁ -C₂ alkoxy,

trifluoromethyl, and

thiomethyl:

R¹ and R₂ are the same or different and are:

C₁ -C₄ alkyl,

cyclohexyl,

C₇ -C₉ aralkyl,

phenyl, or phenyl substituted with one or more members of the groupconsisting of:

chlorine,

methoxy,

methyl, and

trifluoromethyl: or

R¹ and R₂ together are C₄ -C₇ alkylene or C₄ -C₆ oxydialkylene.

Most preferred compounds for plant growth regulatory purposes include:

1-methyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-ethyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-n-propyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-n-butyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-[2-methyl]phenyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isopropyl,N-[4-chloro]phenyl)carbamyl]-5(4H)-tetrazolinone,-(2-methyl)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-4H)-tetrazolinone,

1-(2-methoxy)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-(2,6-dimethyl)phenyl-4-[(N-isopropyl,N-phenyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-trifluoromethyl)phenyl-4-[(N-propyl,N-isopropyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-methyl)phenyl-4-[(N,N-diisopropyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-ethyl)phenyl-4-[(N,N-diethyl)carbamyl]-5(4H)-tetrazolinone,

1-(2-methoxy)phenyl-4-[(N,N-diisobutyl)carbamyl]-5(4H)-tetrazolinone,

1-phenyl-4-[(N-isobutyl,N-isopropyl)carbamyl]-5(4H)-tetrazolinone, and

1-phenyl-4-[(N-ethyl,N-hexyl)carbamyl]-5(4H)-tetrazolinone.

The compounds of this invention are prepared by reacting a tetrazolinonecompound having the formula: ##STR3## wherein M is hydrogen or alkalimetal (such as Li, Na or K) and R is as defined above with a carbamoylhalide having the formula XCONR¹ R², wherein X is chlorine or bromineand R¹ and R₂ have the meanings above.

When M is hydrogen, the reaction is preferably conducted in the presenceof a suitable acid acceptor such as pyridine or a tertiary amine (e.g.,triethylamine). It is noted that this tetrazolinone compound may besynthesized by the methods disclosed in the Horwitz et al and Tsuge etal references mentioned above. The equivalent ratio of X/M (asrepresentative of the above reactants) may vary from about 0.75/1 toabout 2/1, preferably from about 0.9/1 to about 1.5/1. Excess of M maybe advantageous in the purification of product since the M-typetetrazolinone is soluble in base. The reaction temperature may rangefrom about 40° C. to the boiling point of the solvent used. Typically,the reaction is conducted under reflux conditions. Suitable solvents arethose which are inert to the reactant, such as acetone, acetonitrile,toluene, chloroform and the like. The reaction time may vary fromseveral minutes or less to several hours or more depending on factorssuch as reaction batch size, reaction temperature, and the like.

The instant invention is also directed to a composition comprising thesubstituted tetrazolinone compound of this invention and a carriertherefor. The carrier employed in one preferred embodiment of thisinvention is a finely-divided or granular inorganic or organic materialsuch as attapulgite clay, sand, vermiculite, ground corn cobs, activatedcarbon and the like. The compound of this invention may be impregnatedon the finelydivided or granular material.

The carrier may also be an inert powder. Preferably, the inert powder isone of the mineral silicates, e.g., mica, talc, pyrophyllite and clays.In this case, the composition is formed by grinding the compound of thisinvention into a fine powder and mixing it with the inert powder towhich a surface active dispersing agent has been added.

A third carrier is the combination of the above inert powder and water.This carrier employs the wettable powder dispersed in water.

Yet another carrier is a solvent and water. In this embodiment thecompound of this invention is dissolved in a solvent such as benzene,toluene or other aliphatic or aromatic hydrocarbon. An emulsifiableconcentrate is formed with the addition of a surface active and/ordispersing agent. The emulsifiable concentrate is then dispersed inwater. In this composition water solubility may be increased using acosolvent system involving acetone, dimethyl sulfoxide or other watermiscible solvent.

It is noted that the surface active agents preferred for use in thecomposition of this invention are well known to those skilled in theart. In addition, suitable surface active agents for use in thecomposition of this invention are provided in McCutcheon's Detergentsand Emulsifiers, 1970, Allured Publishing Corp., Ridgewood, N.J.; U.S.Pat. No. 2,614,916, columns 2 to 4: and U.S. Pat. No. 2,547,727, columns3 and 4.

The present invention is furthermore directed to a method of controllingweeds, both pre-emergence and post-emergence, by application of aherbicidally effective amount of the composition of this invention.

In the case where the composition comprises impregnated granules of thecompound of this invention, application, to control weeds, is byspreading on the soil. The wettable powder may be similarly applied. Inthe case where the wettable powder is dispersed in water, thiscomposition controls weeds by spraying the dispersion on weeds orunwanted vegetation or onto the soil surface. Where an emulsion isformed that emulsion is likewise sprayed onto the weeds or onto the soilsurface.

When employed as a herbicide, the concentration of the compound of thisinvention in the composition of this invention may vary widely, e.g.from 1 to 95%. The concentration of active compound in dispersionsapplied to the soil or foliage is generally from 0.002% to about 75%.

For use as a pre-emergence herbicide the compound of this invention istypically applied at rates of from about 0.05 to about 25 pounds peracre (from about 0.056 to about 28 kg/ha) to soil which contains weedand crop seed, namely either to the surface of the soil or incorporatedinto the upper one to three inches (2.5 to 7.5 cm.) of soil. As apost-emergence herbicide, the compound is typically applied at rates offrom about 0.05 to about 25 pounds per acre (from about 0.056 to about28 kg/ha) to the foliage of weeds. The compound may be employed singlyor as a mixture of two or more chemicals.

When employed as a herbicide, the most suitable rate of application inany given case will depend on such factors as soil type, soil pH, soilorganic matter content, the quantity and intensity of rainfall beforeand after treatment, the air and soil temperature, light intensity andlight duration per day. All of these factors can have an influence onthe efficacy of the chemicals for a given weed control use.

The herbicide use may include control of vegetation at industrial sitesor selective weed control in crop fields.

In addition, the present invention is directed to a method of regulatingthe growth of plants by the application of a plant growth .regulatoryeffective amount of the composition of this invention. It will beunderstood that the term plant, as used herein, includes plant partssuch as foliage, roots, flower stems and seeds. Depending on the cropvariety, dosage, time of application and certain cultural practices, thegrowth regulating effects which may be obtained include one or more ofthe following: dwarfing, cessation of terminal growth, inhibition ofaxillary and intercalary growth, retardation of internode elongation,inhibition of flowering or reproductive development, and the like.

Compounds of this invention may be used alone, or in combination withone or more pesticidal compositions, or in combination with one or morespray adjuvants (e.g. surface active agents, stickers, spreaders,emulsifiers, suspending agents, or extenders). The amount of activecompound employed follows conventional practice for plant growthregulatory uses, and the chemicals are suitable applied as a formulationin accordance with conventional agricultural chemical practice.

The most suitable dosage of application of the active ingredient(s) forplant growth regulatory effects and the type and amount of adjuvantsubstances to be added to the spray solution will depend on a number offactors, including the plant species; the stage of plant development:the mode of application; the specific biological effect desired; the airand soil temperature; the quantity and intensity of rainfall before andafter treatment: the soil type, pH, fertility and moisture and organicmatter content: the physiological condition and vigor of the targetplants: the relative humidity and wind velocity of the air around thecrop: the extent and density of the foliar canopy of the target plant;the light quality, intensity and duration each day: the type andinterval of previous and subsequent crop protectant chemicalapplications. All of these factors may have an influence on the efficacyof chemicals applied as plant growth regulators. However, one skilled inthe art can, by routine experimentation, readily determine optimumconditions for the employment of any particular compound of thisinvention.

EXAMPLES

The following examples are given to illustrate the invention. Sincethese examples are illustrative of the invention, the invention shouldnot be deemed to be limited thereto.

EXAMPLE 1 Preparation of 1-(2-ethoxyphenyl)-5(4H)-tetrazolinone

Aluminum chloride (15.0 grams, 0.11 mole) was added in small portionswhile stirring to 75 ml of tetrahydrofuran (THF, tested for absence ofperoxide), keeping the temperature of the solution below 30° C.2-Ethoxyphenyl isocyanate (16.2 grams, 0.1 mole), 50 ml THF and 19.5grams, (0.3 mole) of sodium azide were combined in a separate flask,equipped with a condenser and thermometer. The aluminum chloridesolution was added to the flask and the mixture was refluxed at 70° to80° C. for 16 hours. The mixture was cooled to room temperature, and 10ml of concentrated hydrochloric acid and 10 ml of water were added inone portion to the stirred mixture. The mixture was warmed slightly, andnitrogen was swept over the surface to remove unreacted hydrazoic acid.The mixture was stirred for 20 minutes and filtered. The salt was washedtwice with 50 ml portions of THF. The THF layers were combined and afterconcentration under reduced pressure the product crystallized. Afterrecrystallization from ethanol, 10.0 grams (50%) of white confirmed byinfrared (IR) and nuclear magnetic resonance (NMR) analyses.

This compound was subsequently reacted with N,N-dimethylcarbamylchloride resulting in Compound No. 20 of Table I.

EXAMPLE 2 Preparation of1-(2,5-dimethoxyphenyl)-4-(N,N-dimethylcarbamyl)-5(4H)-tetrazolinone(Cpd. No. 19).

Potassium carbonate (6.6 grams, 0.048 mole), 50 ml of acetonitrile and4.4 grams (0.02 mole) of 1-(2,5-di- methoxyphenyl)-5(4H)-tetrazolinonewere combined and refluxed at 85° C. for 15 minutes. The mixture wascooled to room temperature, and 3.2 grams (0.3 mole) of dimethylcarbamylchloride was added in one portion. The mixture was refluxed at 80°-85°C. for one hour, cooled and the salt removed by filtration. After theremoval of the solvent under reduced pressure, the product crystallized.The product was recrystallized from ethanol, giving 4.0 grams (69%yield) of white crystals, m.p. 125°-6° C.

The structure was confirmed by IR and NMR spectra.

EXAMPLE 3 Preparation of1-phenyl-4-(N,N-diethylcarbamyl)-5(4H)-tetrazolinone (Cpd. No. 2)

1-Phenyl-5(4H)-tetrazolinone (4.8 grams, 0.03 mole), 5.4 grams (0.04mole) of potassium carbonate and 50 ml of acetonitrile were combined andrefluxed at 80° C. for 10 minutes. The mixture was cooled to roomtemperature, and 5.4 grams (0.04 mole) of diethylcarbamyl chloride wasadded in one portion. The reaction mixture was refluxed at 80°-90° C.for 16 hours, cooled, and salt removed by filtration. The filtrate waspoured into 75 ml of H₂ O, and a white precipitate was formed. Theproduct was recrystallized from 25 ml of ethanol and 5 ml of hexane,giving 4.5 grams (57% yield) of white crystals, m.p. 66°-8° C. Thestructure was confirmed by IR and NMR-spectra.

As essentially described above, a series of chemicals of this inventionwas prepared as summarized in Table I.

                                      TABLE I                                     __________________________________________________________________________     ##STR4##                                                                     Cpd. No.                                                                           R           R.sup.1                                                                           R.sup.2    m.p. °C.                               __________________________________________________________________________     1   C.sub.6 H.sub.5                                                                           CH.sub.3                                                                          CH.sub.3   114-115                                        2   "           C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                          66-68                                          3   "           i-C.sub.3 H.sub.7                                                                 i-C.sub.3 H.sub.7                                                                        77-78                                          4   "           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                          94-96                                          5   "           C.sub.6 H.sub.5                                                                   C.sub.6 H.sub.5                                                                          140-141                                        6   2-FC.sub.6 H.sub.4                                                                        CH.sub.3                                                                          CH.sub.3   161-163                                        7   2-ClC.sub.6 H.sub.4                                                                       "   "          126-128                                        8   3-ClC.sub.6 H.sub.4                                                                       "   "          110-112                                        9   4-ClC.sub.6 H.sub.4                                                                       "   "          144-145                                       10   2,4,5-Cl.sub.3C.sub.6 H.sub.2                                                             "   "          145-147                                       11   4-CH.sub.3C.sub.6 H.sub.4                                                                 "   "          127-128                                       12   4-CH.sub.3C.sub.6 H.sub.4                                                                 C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                          64-67                                         13   3,4-(CH.sub.3).sub.2C.sub.6 H.sub.3                                                       CH.sub.3                                                                          CH.sub.3   99-101                                        14   2,4,6-(CH.sub.3).sub.3C.sub.6 H.sub.2                                                     "   "          94-96                                         15   3-CF.sub.3C.sub.6 H.sub.4                                                                 "   "          80-82                                         16   4-CH.sub.3 OC.sub.6 H.sub.4                                                               "   "          145-147                                       17   2,4-(CH.sub.3 O).sub.2C.sub.6 H.sub.3                                                     "   "          126                                           18   3,4,5-(CH.sub.3 O).sub.3C.sub.6 H.sub.2                                                   "   "          136-138                                       19   2,5-(CH.sub.3 O).sub.2C.sub.6 H.sub.3                                                     "   "          125-126                                       20   2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                          63-64                                         21   2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        CH.sub.3                                                                          CH.sub.3   87-89                                         22   2-C.sub.2 H.sub.5 OOCC.sub.6 H.sub.4                                                      "   "          76-78                                         23   4-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                        "   "          110-112                                       24   3,4-Cl.sub.2C.sub.6 H.sub.4                                                               "   "          147-149                                       50   2-CH.sub.3 SC.sub.6 H.sub.4                                                               i-C.sub.3 H.sub.7                                                                 i-C.sub.3 H.sub.7                                                                        95-96                                         51   CH.sub.3    "   C.sub.6 H.sub.5                                                                          84-86                                         52   C.sub.2 H.sub.5                                                                           "   "          77-79                                         53   n-C.sub.3H.sub.7                                                                          "   "          41-43                                         56   n-C.sub.4H.sub.9                                                                          "   "          oil                                           57   CH.sub.2 C.sub.6 H.sub.5                                                                  "   "          70-71                                         58   C.sub.6 H.sub.5                                                                           CH.sub.3                                                                          "          94-97                                         59   "           i-C.sub.3 H.sub.7                                                                 "          102-3                                         60   "           "   2-CH.sub.3 C.sub.6 H.sub.4                                                               102-3                                         61   "           "   4-CH.sub.3 C.sub.6 H.sub.4                                                               93-95                                         62   "           "   2-OCH.sub.3 C.sub.6 H.sub.4                                                              103-4                                         63   "           "   4-OCH.sub.3 C.sub.6 H.sub.4                                                              100-1                                         64   "           "   2-ClC.sub.6 H.sub.4                                                                      119-21                                        65   "           "   3-ClC.sub.6 H.sub.4                                                                      79-81                                         66   "           "   4-ClC.sub.6 H.sub. 4                                                                     105-6                                         67   "           "   3-CF.sub.3 C.sub.6 H.sub.4                                                               88-89                                         68   "           "   2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                     108-9                                         69   "           "   2,6-(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.3                                              94-96                                         71   2-CH.sub.3C.sub.6 H.sub.4                                                                 "   C.sub.6H.sub.5                                                                           95-97                                         72   2-C.sub.2 H.sub.5 C.sub.6 H.sub.4                                                         "   C.sub.6 H.sub.5                                                                          86-88                                         73   2-iC.sub.3 H.sub.7 C.sub.6 H.sub.4                                                        "   "          oil                                           74   2-CH.sub.3 OC.sub.6 H.sub.4                                                               "   "          101-2                                         75   2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                        "   :          65-67                                         76   2,6-(CH.sub.3).sub.2 C.sub.6 H.sub.3                                                      "   "          74-76                                         77   2,6-(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.3                                               "   "          81-82                                         78   1-naphthyl  "   "          137-8                                         79   CH.sub.3 CH.sub.2                                                                         "   3,4-OCH.sub.2 OC.sub.6 H.sub.3                                                           93-94                                         __________________________________________________________________________

Following essentially the procedures outlined above additional compoundswithin the scope of this invention are prepared. These compounds,compounds 25-46, are defined in Table II.

                  TABLE II                                                        ______________________________________                                        Cpd.                                                                          No.  R              R.sup.1     R.sup.2                                       ______________________________________                                        25   CH.sub.3       CH.sub.3    CH.sub.3                                      26   n-C.sub.6 H.sub.13                                                                           C.sub.4 H.sub.9                                                                           C.sub.6 H.sub.13                              27   C.sub.6 H.sub.5 --C(CH.sub.3).sub.2                                                          C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                               28   4-CH.sub.3 --C.sub.6 H.sub.4 --CH.sub.2                                                      "           "                                             29   2-F--C.sub.6 H.sub.4 --CH.sub.2                                                              C.sub.6 H.sub.11                                                                          "                                             30   4-Cl--C.sub.6 H.sub.4 --CH.sub.2                                                             CH.sub.2 CH═CH.sub.2                                                                  CH.sub.2 CH═CH.sub.2                      31   CH.sub.3 OCH.sub.2                                                                           CH.sub.3    CH.sub.3                                      32   C.sub.12 H.sub.25 OCH.sub.2                                                                  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                               33   2-Br--C.sub.6 H.sub.4 --CH.sub.2                                                             C.sub.12 H.sub.25                                                                         CH.sub.3                                      34   4-C.sub.4 H.sub.9 --C.sub.6 H.sub.4 --CH.sub.2                                               C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                               35   3-CH.sub.3 O--C.sub.6 H.sub.4 --CH.sub.2                                                     CH.sub.3    CH.sub.3                                      36   4-C.sub.6 H.sub.5 O--C.sub.6 H.sub.4 --CH.sub.2                                              C.sub.2 H.sub. 5                                                                          C.sub.2 H.sub.5                               37   3,4-(CH.sub.2 O.sub.2)C.sub.6 H.sub.3 CH.sub.2                                               CH.sub.3    CH.sub.3                                      38   2,3-(CH.sub.2 O.sub.2)C.sub.6 H.sub.3                                                        "           "                                             40   (Cl.sub.3 CO)C.sub.6 H.sub.4                                                                 i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                             41   3-CF.sub.3 --C.sub.6 H.sub.4 --CH.sub.2                                                      CH.sub.3    CH.sub.3                                      42   3-NO.sub.2 --C.sub.6 H.sub.4                                                                 "           "                                             43   3-CN--C.sub.6 H.sub.4                                                                        --(CH.sub.2).sub.6 --                                     44   2-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4                                                        C.sub.5 H.sub.9                                                                           CH.sub.3                                      45   2-(COOH)--C.sub.6 H.sub.4                                                                    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                               46   C.sub.6 H.sub.11                                                                             C.sub.3 H.sub.7                                                                           C.sub.3 H.sub.7                               ______________________________________                                    

EXAMPLE 4

To illustrate the effectiveness of the previously described substitutedtetrazolinones of this invention as pre-emergence herbicides, 300 mgchemical was dissolved in a composition comprising 10 ml acetone towhich 30 mg emulsifying agent, ethoxylated sorbitan monolaurate, wasadded. The solution was diluted to 100 ml with distilled water. Tenmilliliters of this 3000 ppm solution was diluted to 250 ppm withdistilled water. The chemical was applied at the rate of 10 pounds/acre(11.2 kg/ha) by drenching 46 ml of the 250 ppm solution on the surfaceof soil in 41/2 inch (11.25 cm) plastic pots wherein seeds of thefollowing weeds had been planted: velvetleaf (Abutilon theophrastimedic) (VL), jimsonweed (Datura stramonium L.) (JW), tall morning glory(Ipomea purpurea L. Roth) (TM), switchgrass (Panicum virgatum L.) (SG),barnyardgrass (Echinochloa crusgalli (L.) Beauv.) (BG), green foxtail(Setria viridis (L.), Beauv.) (GF). The percent control of the weedscompared to untreated checks was determined two weeks after treatment.TABLE III summarizes the results achieved with compounds formulated asindicated above, and the data clearly indicate the good to excellentherbicidal efficacy of compounds of this invention.

                  TABLE III                                                       ______________________________________                                        Preemergence Activity                                                         (Percent Control at 11.2 kg/ha)                                               Cpd. No.                                                                              VL      JW      TM    BG    SG    GF                                  ______________________________________                                         1      0       0       0     100   100   100                                  2      0       0       0     100   100   100                                  3      0       0       0     100   100   100                                  4      0       0       0     100   100   100                                  5*     --      --      --    50    50    0                                    6      50      30      50    100   100   100                                  7      0       0       0     100   100   100                                  8      90      0       0     100   95    95                                   9      0       0       0     75    100   80                                  10      0       0       0     75    95    100                                 11      0       0       0     98    100   100                                 12      0       0       0     100   100   100                                 13      0       0       0     100   100   100                                 14      0       0       0     100   100   100                                 15      0       0       0     100   100   100                                 16      0       0       0     100   100   100                                 17      0       0       0     100   100   100                                 18      0       0       0     100   100   100                                 19      50      0       25    100   100   100                                 20      --      --      --    100   100   100                                 21      25      0       0     100   100   100                                 22      50      75      0     100   100   100                                 23      100     0       0     90    95    25                                   24*    0       0       0     40    50    20                                  50      0       0       0     95    95    100                                 51      100     100     100   100   100   100                                 52      100     100     100   100   100   100                                 53      75      100     100   100   100   100                                 58      0       0       0     50    50    75                                  59      0       0       0     80    95    100                                 60      0       0       25    60    100   100                                 61      0       0       50    100   100   100                                 62      0       90      0     75    100   100                                 63      0       0       0     95    90    100                                 64      0       75      85    100   100   100                                 65      50      0       0     100   100   100                                 66      95      100     0     100   100   100                                 67      0       0       0     100   100   100                                 76      0       50      100   100   100   100                                 77      0       0       95    100   100   100                                 79      80      60      100   100   100   100                                 ______________________________________                                         *Tested at 22.4 kg/ha                                                    

EXAMPLE 5

To illustrate effectiveness of the described substituted tetrazolinonesas post-emergence herbicides, the 3000 ppm solution described underExample 4 was atomized with a conventional DeVilbiss [trademark]sprayer, wetting the foliage to the drip point. The weeds, which werethe same species as described under Example 4, were treated six daysafter emergence. The percent weed control was evaluated two weeks aftertreatment. Table IV illustrates the postemergence herbicidal efficacy ofchemicals of this invention.

                  TABLE IV                                                        ______________________________________                                        Postemergence Activity                                                        (Percent Control at 3000 ppm)                                                 Cpd. No.                                                                             VL     JW       TM    BG     SG    GF                                  ______________________________________                                         1*    0      0        35    85     95    90                                   2     0      0        5     100    75    100                                  3     10     0        25    5      0     15                                   4     0      5        5     80     25    45                                   5*    90     100      10    0      90    95                                   6     0      0        5     55     5     25                                   7     15     10       5     35     15    15                                   8     0      15       30    90     10    100                                  9     0      0        10    75     90    75                                  10     0      0        10    60     --    75                                  11     0      5        25    85     95    90                                  12     0      0        35    85     20    50                                  13     0      0        25    80     85    75                                  14     75     0        40    50     85    20                                  15     50     95       100   100    100   100                                 16     0      0        50    40     60    55                                  17     15     0        10    0      0     0                                   18     0      5        5     20     0     10                                  19     0      0        5     10     15    5                                   20     --     70       85    95     --    90                                  21     5      65       45    25     75    15                                  22     5      0        35    50     10    15                                  23     25     50       90    85     --    65                                  24     0      0        0     40     50    15                                  50     0      0        0     5      0     5                                   51     10     26       60    50     10    50                                  53     0      0        15    95     95    100                                 59     0      0        5     80     0     60                                  61     0      0        10    10     0     5                                   64     0      0        30    10     0     10                                  71     0      0        5     15     0     5                                   74     0      0        25    20     0     10                                  75     0      0        5     20     10    15                                  76     0      0        10    10     0     0                                   77     0      0        5     15     0     10                                  ______________________________________                                         *Control at 6000 ppm                                                     

Similar pre- and post-emergence herbicidal results are achieved withCompound Numbers 25-46 when applied to weeds in a manner indicated inExamples 4 and 5.

EXAMPLE 6 Retardation of Plant Growth

To illustrate the effectiveness of the described compounds as plantgrowth regulants, 600 mg of chemical were dissolved in a 10 ml organicsolvent comprising acetone to which 30 mg of an emulsifying agent,"Tween 20" (trademark) (an ethoxylated sorbitan monolaurate), was added.This solution was diluted to 200 ml with distilled water, producing a3000 ppm solution/suspension. By appropriate dilutions with distilledwater, 1000 and 500 ppm solution/suspensions were prepared. The spraysolution/suspensions were atomized with a DeVilbiss (trademark) No. 152sprayer and wetted the foliage to the drip point of soybean plants(Glycine max (L.) Merr., cv. Williams, 2 weeks old), cotton plants(Gossypium hirsutum L. cv. Stoneville 213, 3-4 weeks old), bean plants(Phaseolus vulgaris L. cv. Pinto III, 2 weeks old), barley plants(Hordeum vulgare L. cv. Herta, 1 week old) and rice plants (Oryza sativaL. cv. Nato, 1 week old). After 1 to 3 weeks (depending on plantspecies) in a greenhouse, the plants were evaluated for retardation ofvegetative growth. A summary of growth retardation data appears in TableV.

                  TABLE V                                                         ______________________________________                                        Percent Plant Growth Retardation                                              Cpd. Barley    Bean     Cotton  Soybean                                                                              Rice                                   No.  3000 ppm  1000 ppm 3000 ppm                                                                              3000 ppm                                                                             1000 ppm                               ______________________________________                                         3   0         100      100     0      --                                      4   0         0        50      0      --                                      5   0         0        100     0      --                                     10   0         50       50      0      --                                     14   25        80       50      80     --                                     17   0         0        0       30     --                                     19   0         0        0       0      35                                     20   0         80       80      0      --                                     21   0         30       0       0      45                                     22   0         60       50      0      --                                     50   0         90       85      95     --                                     51   80        100      100     100    --                                     52   80        100      100     100    --                                     53   0         100      90      100    --                                     57   0         100      75      100    --                                     58   0         90       50      0      --                                     59   30        100      90      90     --                                     60   0         90       80      80     --                                     61   0         60       *90     100    --                                     62   0         100      60      80     --                                     63   25        50       80      80     --                                     64   0         100      100     95     --                                     65   30        100      95      90     --                                     66   0         100      100     90     --                                     67   100       100      90      90     --                                     71   50        100      50      100    --                                     72   100       100      100     100    --                                     73   0         100      100     95     --                                     74   30        100      90      95     --                                     75   15        80       90      90     --                                     76   0         100      100     75     --                                     77   0         100      0       90     --                                     78   0         0        90      75     --                                     79   50        100      --      100    --                                     ______________________________________                                         -- Indicates not tested                                                       *Tested at 500 ppm                                                       

EXAMPLE 7 Inhibition of Axillary Branch Growth in Beans

Pinto bean plants were grown in the greenhouse until they had 1 to 3trifoliate leaves. The stem was cut off at 2 or 3 cm above the primaryleaves, and the branches in those leaf axils were removed. Spraysolution/suspensions were prepared and applied in a manner similar tothat described in Example 6. After 10-12 days in the greenhouse, anyaxillary branch growth was removed and weighted, and the percentage ofgrowth control was calculated. A summary of these results appear inTable VI.

                  TABLE VI                                                        ______________________________________                                        Axillary Growth Control of Beans                                              (at 1000 ppm)                                                                 Cpd. No. Control, %    Cpd. No. Control, %                                    ______________________________________                                         1       85            52       100                                            2        7*           53       27                                             3       96            57       97                                             4       96            58        20*                                           5        62*          59       100                                            7       88            60       76                                             8       86            61       86                                             9       100           62       87                                            11       94            63       97                                            12       97            64       99                                            13       99            65       97                                            14       96            66       99                                            16       75            67       86                                            17       72            71       100                                           18       64            72       97                                            19       31            73       100                                           20        44*          74       74                                            24       61            75       56                                            50       96            78       100                                           ______________________________________                                         *Tested at 400 ppm                                                       

The above embodiments and examples illustrate the scope and spirit ofthe instant invention. These embodiments and examples will make apparentto those skilled in the art, other embodiments and examples within thescope of the present invention. Therefore, the instant invention shouldbe limited only by the appended claims.

What is claimed:
 1. A process for making a compound having the formula:##STR5## wherein R is:C₁ -C₁₂ alkyl, C₂ -C₁₃ alkoxyalkyl, C₇ -C₉aralkyl, C₅ -C₆ cycloalkyl, C₃ -C₁₂ alkenyl, naphthyl, phenyl, phenylsubstituted with at least one member selected from the group consistingof:fluorine, chlorine, bromine, iodine, C₁ -C₄ alkyl, C₁ -C₄ alkoxy,methylenedioxy, NR³ R⁴ wherein R³ and R⁴ are the same or different andare hydrogen or C₁ -C₆ alkyl, C₂ -C₅ alkoxycarbonyl, carboxy, phenoxy,nitro, cyano, trihalomethyl wherein halo is fluorine, chlorine orbromine, trihalomethoxy wherein halo is fluorine, chlorine or bromine,C₁ -C₆ alkylthio, and C₁ -C₆ fluoroalkylthio; or benzyl substituted withat least one member selected from the group consisting of:fluorine,chlorine, bromine, iodine, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, methylenedioxy,C₂ -C₅ alkoxycarbonyl, phenoxy, nitro, cyano, trihalomethyl wherein halois fluorine, chlorine or bromine, trihalomethoxy wherein halo isfluorine, chlorine or bromine, C₁ -C₆ alkylthio, and C₁ -C₆fluoroalkylthio; R¹ and R₂ are the same or different and areC₁ -C₆alkyl, C₃ -C₆ alkenyl, C₅ -C₆ cycloalkyl, C₇ -C₉ aralkyl, C₇ -C₉ aralkylsubstituted with at least one member selected from the group consistingof:fluorine, chlorine, bromine, iodine, C₁ -C₆ alkyl, C₁ -C₂ haloalkylwherein halo is fluorine, chlorine or bromine, halomethoxy wherein halois fluorine, chlorine or bromine, C₁ -C₆ alkoxy, C₁ -C₆ alkylthio, C₁-C₆ fluoroalkylthio, phenoxy, phenylthio, carboxy, C₂ -C₅alkoxycarbonyl, methylenedioxy, nitro, cyano, and NR⁷ R⁸ wherein R⁷ andR⁸ are the same or different and are hydrogen, C₁ -C₆ alkyl, C₄ -C₈alkylene or C₄ -C₈ oxydialkylene; naphthyl, phenyl, or phenylsubstituted with at least one member selected from the group consistingof: fluorine, chlorine,bromine, iodine, C₁ -C₆ alkyl, C₁ -C₂ haloalkylwherein halo is fluorine, chlorine or bromine; halomethoxy wherein halois fluorine, chlorine or bromine, C₁ C₆ alkoxy, C₁ -C₆ alkylthio, C₁ -C₆fluoroalkylthio, phenoxy, phenyl, phenylthio, carboxy, C₂ -C₅alkoxycarbonyl, C₁ -C₂ alkylenedioxy, optionally substituted with 1-2methyl groups, C₁ -C₂ alkyleneoxy, optionally substituted with 1-2methyl groups, nitro, cyano, and NR⁷ R⁸ wherein R⁷ and R⁸ are the sameor different and are hydrogen, C₁ -C₆ alkyl, C₄ -C₈ alkylene or C₄ -C₈oxydialkylene; or R¹ and R₂ together are C₄ -C₈ alkylene or C₄ -C₈oxydialkylene, with the proviso that when R is other than C₃ -C₁₂alkenyl, C₁ -C₆ alkylthio-substituted phenyl, C₁ -C₆alkylthio-substituted benzyl, C₁ -C₆ fluoroalkylthio-substituted phenylor benzyl and wherein at least one of R¹ and R₂ is C₇ -C₉ aralkyl, C₇-C₉ substituted aralkyl phenyl or substituted phenyl, whereinsubstitution is as indicated above, comprising: the step of reacting, inan inert solvent at a temperature range from about 40° C. up to theboiling point of said solvent a tetrazolinone compound having theformula: ##STR6## wherein R has the meanings given above and wherein Mis hydrogen with an alkali metal carbonate to form an intermediate ofthe formula above wherein M is Li, Na or K followed by the reaction ofsaid intermediate with a carbamoyl halide having the formula XCONR¹ R²,wherein X is chlorine or bromine and R¹ and R₂ have the meanings above.2. A process in accordance with claim 1 where the equivalent ratio ofX/M is in the range of 0.75 to 2/1.
 3. A process in accordance withclaim 1 wherein said equivalent ratio of X/M is in the range of 0.9 to1.5/1.